Aliphatic sulfonation

Introduction of the sulfonic acid group by replacement of hydrogen is much less important in the aliphatic than in the aromatic series. On direct sulfonation of alkanes by sulfuric acid, oleum, or sulfur trioxide side reactions (isomerization, dehydrogenation, oxidation, and formation of sulfone bonds) occur to such an extent that this process has found hardly any practical applications. 

A more straightforward formation of sulfonic acids by means of sulfuric acid has been observed with aliphatic carbonyl compounds, acids, etc. 

Rewald97 treated ( )-camphor (100 g) with a mixture of acetic anhydride (135 g) and concentrated sulfuric acid (98 g) and after 4 days obtained optically inactive camphorsulfonic acid in a yield that amounted to 40% after recrystallization from glacial acetic acid. 

Sulfonation of fatty acids by sulfuric acid usually affords a-sulfo carboxylic acids in only moderate yield but the yield is said to be almost quantitative if a little pyridine is present during the reaction.98 

Chlorosulfonic acid, and in particular adducts of sulfur trioxide with dioxan or pyridine have been used for aliphatic sulfonation. These adducts, which are to be considered as betaine-like internal oxonium salts, very easily transfer 

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Some green algae are able to use aromatic sulfonic acids (Figure 2.4a) (Soeder et al. 1987) and aliphatic sulfonic acids (Figure 2.4b) (Biedlingmeier and Schmidt 1983) as sources of sulfur. Cultures of Scenedesmus obliquus under conditions of sulfate limitation metabolized naphthalene-l-sulfonate to l-hydroxy-naphthalene-2-sulfonate and the gluco-side of naphth-l-ol (Kneifel et al. 1997). These results are consistent with formation of a 1,2-epoxide followed by an NIH shift. 

As an example of esters of aliphatic sulfonic acids trifluoromethylsulfonic imidazo-lide has been treated with various phenols to give phenyl sulfonic esters [U1... 

Aliphatic solvents, alkyllithium compounds and, 14 250-251 Aliphatic sulfonates, 26 145 Aliquot samples, 13 413-415 analysis of, 13 416 Aliskren, 5 158 Alitame, 12 42 24 232 Alite, phase in Portland cement clinker, 5 471, 472t, 473t Alitretinoin, 25 790 Alizarin, color of, 7 331 Alizarin derivatives, 9 337 Alizarin pure Blue B, 4 361t Alkadienes, metathesis of, 26 923 Alkali/alkaline-earth cation recognition,... 

Sulfitation and Bisulfitation of Unsaturated Hydrocarbons. Sulfites and bisulfites react with compounds such as olefins, epoxides, aldehydes, ketones, alkynes, aziridines, and episulfides to give aliphatic sulfonates or hydroxysulfonates. These compounds can be used as intermediates in the synthesis of a variety of organic compounds. 

Alkyl iodides. Although this mixture reduces arsenesulfonic acids, it converts aliphatic sulfonic acids,1 suliinic acids, thiols, sulfonates, and disulfides to alkyl iodides in 70 100% yield.2... 

Polystyrene-bound aliphatic sulfonic esters and O-aryl sulfamates can be cleaved by treatment with potassium carbonate or other nucleophiles, whereby the corresponding alcohols are released into solution (Entries 11 and 12, Table 3.34). O-Alkyl sulfamates, on the other hand, do not react with nucleophiles and cannot be used as linkers for alcohols [245],... 

XTec SAX (3 pm) Separation of inorganic anions (F, CIO3", HCOO, Cl, Br", SO42, SCN", CIO42 ) and aliphatic sulfonates Varying concentrations of phosphate buffer pH 7.2, sulfate buffer pH 8.2, and nitrate buffer pH 6.8 [91]... 

Aliphatic sulfonic acids are reduced to alkyl iodides by reaction with PPh3/I21089. 

Methyisuifbnyimethane) (aliphatic sulfone) Dimethyl sulfoxide (asparagus) [aerial] reputed aphrodisiac Asparagus officinalis (Liliaceae) Pungent (urine)... 

Other related reactions are the substitutions of aliphatic sulfonate esters by arenes and the epoxide-opening with benzenes catalyzed by gold. In both cases, the aryl groups are the nucleophiles that attack the gold-coordinated sulfonate esters or epoxides, respectively. 

The major subgroups of anionic surfactants include the alkali carboxylates (soaps), sulfates, sulfonates, and to a smaller degree, phosphates. The esterification of alcohol with sulfuric acid yields probably the best-studied surfactant, sodium dodecylsulfate or SDS. SDS, a sulfate ester, is an extremely effective emulsifier because of its high-electrostatic repulsion. Other sulfates are, for example, sulfated esters from fatty acids, sulfated ethers, and sulfated fats and oils. Sulfonates stem from the reaction of sulfonic acid with suitable substrates. Members of the class of sulfonates are, for example, sulfonic acid salts or aliphatic sulfonates. Other anionic surfactants include substances such as carboxylated soaps and esters of phosphoric acid. 

Glycine derivatives and aliphatic sulfonates are examples of compounds that can function in this way. The use of these inhibitors in cooling systems is usually limited by thek biodegradabflity and thek toxicity toward fish. In addition, they can form thick, oily surface films, that may severely retard heat transfer. 

Simple aliphatic sulfones, RS02R are polarographically inactive both in pro tic and aprotic media methylene disulfones are, however, reducible in DMF at potentials close to the decomposition potential of the medium. S-Disulfones and benzyl sulfones are rather acidic and may function as proton donors during the reduction, and their anions are generally not reducible [150]. Alkyl aryl sulfones and diaryl sulfones are reducible under protic and aprotic conditions [151-154] during the reduction of long chain aryl alkyl sulfones the EGB may induce a 6-cleavage, and in some cases dimerized products are observed [155]. The electrochemistry of sulfones has been reviewed by Chambers [103] and Simonet [156]. 

When run in nonpolar solvents, the reaction is stoichiometric in the formation of both aliphatic and aromatic sulfoxides and aliphatic sulfones. 

Both these reagents will react with alkyl halides in aqueous media to give the corresponding sulfonic acids (21). This procedure has been used extensively for the preparation of aliphatic sulfonic acids in good yields (see Chapter 7, p. 100). Sodium hydrogen sulfite will also form sulfonic acids by addition to alkenes in the presence of peroxide catalysts (anti-Markownikoff reaction) (Scheme 19). 

The majority of aliphatic compounds tend to be resistant to direct sulfonation and under forcing conditions often form a complex mixture of products. Consequently, aliphatic sulfonic acids are generally prepared by other methods, such as treatment of an alkyl halide with sodium sulfite (see p. 101). However, in certain cases direct sulfonation works well, namely with terminal alkynes (36) and tertiary alkanes (37) (Scheme 19). 

Dehydration of sulfonic acids. The reagent converts aromatic and aliphatic sulfonic acids into their anhydrides in high yield." It is preferred to DCC for this purpose because the resulting urea is less soluble in benzene and easily separated from the anhydride. 

The results demonstrated that several of the fluoro- aliphatic sulfones (I, II, III, XXV, and XXXIV) are suitable as bait-toxicants for control of the fire ant and have activity comparable to the currently available bait toxicant (Amdro). 

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